New composition of matter and method of making same



Patented Dec. 24, 1940 2,226,115 FICE NEW COMPOSITION OF MATTER ANDMETHOD OF MAKING SAlVIE Melvin De Groote, University City, BernhardKeiser, Webster Groves, and Arthur F. Wirtel, Kirkwood, M0., assignors,by mesne assignments, to Petrolite Corporation, Ltd., a corporation ofDelaware No Drawing. Application May 12, 1939, Serial No. 273,220

13 Claims.

This invention relates to materials, compounds and compositions ofmatter of the kind that are used to treat emulsions of mineral oil andwater, such as petroleum emulsions, for the v purpose of separating theoil from the water.

vOne object of our invention is to provide a new material or compositionof matter, thatis particularly adapted for resolving petroleum emulsionsof the water-in-oil type, that are commonly referred to as cut oil,roily oil, emulsified oil, etc, and which comprise fine droplets ofnaturally-occurring waters or brines dispensed in a more or lesspermanent state throughout the oil which constitutes the continuousphase of the emulsion.

Another object of our invention is to provide a method by which said newmaterial or composition of matter can be manufactured readily andeconomically.

0 While the new material or composition of matter which constitutes ourpresent invention is particularly adapted for use as a demulsifier inthe resolution of petroleum emulsions, it may have uses in other artsthat we have not yet investigated. As will be pointed out hereinafter,the method of making said new compound or composition of matter is suchthat it is accompanied by certain cogeneric materials. The previouslyindicated-objectsof our invention are 30 specifically intended to applynot-only to the principal product of reaction hereinafter describedentirely or partially by chemical formulae, but also to the cogenericmixture obtained in the manner and by the methods hereinafter described.

The new compound or composition of matter which constitutes one featureof our present invention consists of a certain kind of ester orcondensation product or polymerization product, derived by reactionbetween a polybasic carboxy acid, or its obvious functional equivalent,such as phthalic anhydride, and an acylated tertiary methylene diamine.The diamine that is employed is of the kind characterized by thepresence of at least one oxy-acyl radical derived from a detergentforming monocarboxy acid linked to an amino nitrogen atom by ahydrocarbon radical, or its obvious functional equivalent, such as ahydrocarbon radical, interrupted at least once by an oxygen atom; saidacylated tertiary methylene diamine being additionally characterized byhaving at lea-st one alcoholic hydroxyl radical.

As to comparable compositions of matter, in which the diamine does notcontain as an integral part of the molecule, an oxy-acyl radical derivedfrom a detergent-forming acid, but char acterized by the fact that thepolybasic acid is joined directly or through a suitable intermediate toa detergent-forming acid, reference is made to the co-pending'application for patent, Serial No. 273,223, filed May 12, De Groote andBernhard Keiser, said co-pending application also contemplating the useof the therein described compositions of matter as demul-sifiers for oilfield emulsions.

It is well known that certain monocarboxy organic acids, containingapproximately 8 carbon atoms or more, and not more than 32 carbon atoms,are characterized by the fact that they combine with alkalies to producesoap or soaplike materials. These detergent-forming acids include fattyacids, resin acids, petroleum (naphthenic) acids, etc. For sake ofconvenience, these acids will be indicated by the formula R.COOH.

It is also well known that diamines, and particularly those havingpronounced basic properties, may be derived by various means, providedthat the resultant diamine is characterized by'the fact that the twoamino nitrogen 7 atoms are not attached to the same carbon atom. Suchdiamines, generally referred to as alkylene diamines, are well known andmay be characterized by ethylene diamine. The present invention does notcontemplate the use of diamines I Derivatives of the diamines herein ofthis type. contemplated are characterized by being a methylene diaminederivative, i. e., a derivative of the hypothetical methylene diamineMethylene diamine is almost unknown for practical purposes, since it isvery unstable in the in which E represents an alkyl, aralkyl, alicyclic,aryl, alkylol, aralkylol, hydroxy alicyclic, heterocyclic, or otherequivalent radical; and B" an alkylol, aralkylol, hydroxy alicyclic, orsimilar radical. Similarly, the formula B! represents a secondary amine,in which a hydroxy hydrocarbon radical may or may not be 1939, by Melvinpresent as a substituent for an amino hydrogen atom.

It is well known that aldehydes, particularly the aldehydes ofrelatively low molecular weight, such as formaldehyde, acetaldehyde,aldol, furfural, benzaldehyde, phenylacetaldehyde,hexahydro-benzaldehyde, etc., can combine with two moles of a secondaryamine, so. as to yield a methylene diamine, characterized by the factthat the two amino nitrogen atoms are attached to the same carbon atom.Such reaction may be indicated in the following manner:

The amine so produced may be indicated by the following formula:

BI in which T may represent a hydrogen atom de rived from formaldehyde,or may represent a radical derived from acetaldehyde, propionaldehyde,butyraldehyde, heptaldehyde, lauric aldehyde, palmitic aldehyde, orstearic aldehyde, etc. Naturally, B" may occur more than once, and Bless than three times. Similarly, instead of aliphatic aldehydes, onemay employ heterocyclic aldehydes, such as furfuraldehyde, or aromaticaldehydes, such as benzaldehyde, or an aralkyl aldehyde, such asphenylacetaldehyde. One may also employ alicyclic aldehydes, such ashexahydro-benzaldehyde. Unsaturated aldehydes, such as acrolein,crotonaldehyde, or tiglic aldehyde, maybe employed. As previouslyindicated, B may represent radicals, such as methyl, ethyl, propyl,butyl, amyl, hexyl, octyl, decyl, hexadecyl, octadecyl, or similarradicals. Similarly, B may represent an alkyl radical, such as a benzylradical, ethyl benzyl radical, dimethyl benzyl radical, an alicyclicradical, such as the cyclohexyl, methyl cyclohexyl, etc.; likewise, B,as well as B", may represent the radicals hydroxy ethyl, 'hydroxypropyl, hydroxy butyl, and other similar radicals, including aC6H4C2H4OH radical, or, a CsI-ImOI-I radical. Other radicals include thefurfural radical, or hydroxyderivatives thereof. Piperidine may beconsidered as a special adaptation, in Which one radical replaces twoamino hydrogen atoms. As previously indicated, B may be selected fromany of the type of radicals above mentioned; whereas, B" is limited tothose radicals in which there is an alcoholic hydroxy group present,such as an alkylol radical, etc.

It is to be noted that the methylene diamine, expressed by the aboveformula, is a tertiary diamine in the sense that neither amino nitrogenatom has attached thereto a replaceable hydrogen atom. For convenience,the above formula may be rewritten as follows, so as to indicate thatthere is present an alcoholic hydroxyl radical:

in which 3 OH is obviously the monovalent hydroxy hydrocarbon radical,such as an alkylol radical or the like. It is well known that amines,particularly non-aryl, such as triethanol-amine or the like, can beacylated by reaction with fatty acids, or a suitable functionalderivative thereof, such as the acyl chloride, or the anhydride, or eventhe ester. If the tertiary hydroxy methylene diamine of the kind justdescribed is reacted with a detergent-forming monobasic carboxy acid,the reaction may be indicated in the following manner:

\ BOI-I+HOOC.R

with the formation of an intermediate ester, which may be indicated inthe following manner:

Such intermediate ester can only react with polybasic acids, such asphthalic anhydride, provided that there is present at least onealcoholic hydroxyl radical. In order to indicate the various forms ofsuch hydroxylated intermediate ester, attention is directed to thefollowing facts: the hydroxyl radical may be present as part of theradical derived from the detergent-forming monobasic carboxy acid; forinstance, if ricinoleic acid, diricinoleic acid, hydroxy-stearic acid,dihydroxy stearic acid, chlorinoted ricinoleic acid, or the like hadbeen employed, then there would be present an alcoholic hydroxylradical, and the above formula might be rewritten as follows:

Similarly, there might be present, prior to reaction with thedetergent-forming monocarboxy 'acid or its equivalent, more than onehydroxy hydrocarbon radical. For instance, the composition might beindicated thus:

An examination of the previous formulas reveals that the hydroxylatedtertiary acylated methylene diamine must contain at least one hydroxyl,and. might contain as many asnine hydroxyls available foresterification; and as a matter of fact, mig t contain an even greaternumber if, instead of using the secondary amine, such as diethanolamine,dipropanolamine, dibutanolamine, etc., one employedethanolglycerylamine, propyl glycerylamine, or diglycerylamine. Aminesderived from diglycerol instead of glycerol would furnish radicalscontaining three hydroxyls, even after attachment to the amino nitrogenatom. Similarly, the detergent-forming monocarboxy acid radical might bederived from hydroxystearic acid, and thus furnish as many as eightalcoholic hydroxyl radicals. If, in all instances, B and B' are derivedfrom diglycerylamine, there would be present at least sixteen hydroxyls,and there mig t be present at least one more, if aldol or a higherhomologue were employed as a reactant in formation of the intermediateester.

In addition to aldol, other similar hydroxy aldehydes oraldehyde-alcohols may be employed. As to such aldehydes other thanaldol, reference is made to Richters Organic Chemistry, (Allott), volume1, third English edition, 1934, pages 389- 391.

In view of what has been said previously, it does not appear necessaryto enumerate various suitable amines which may be employed, but it maybe well to indicate that among those which may be employed are thefollowing: diethanolamine, dipropanolamine, dibutanolamine,dioctanolamine, dipentanolamine, glyceryl hexanolamine, methylglycerylamine,ethyl giycerylamine, propyl glycerylamine, cyclohexylglycerylamine, benzyl glycerylamine; dibenzylamine, ethyl benzylamine,methyl benzylamine, propyl benzylamine, phenylmonoethanolamine,naphthylmonoethanolamine, cyclohexyl ethylamine, cyclohexyl propylamine,cyclohexyl hexylamine, diethylamine, dipropylamine, diamylamine,dihexylamine, dioctylamine, diglycerylamine, etc. In all the previousexamples each radical indicates a substituent for an amino hydrogenatom. Similarly, amines can be obtained from polyglycerols orpolyglycols, as for instance, the secondary amines, indicated by thefollowing formulas:

Such amines may serve as functional equivalents of the previouslydescribed amines, which happen to be free from an ether linkage.Likewise, one may have amines in which there is more than one etherlinkage, i. e., in which the hydrocarbon radical which replaces an aminohydrogen atom has been interrupted more than once by an oxygen atom.

In examining the previous formulas, it becomes evident that if twodifferent amines are employed, one of which does not contain ahydroxylated hydrocarbon radical, then the reaction is not limited totwo dissimilar amines, but may take place in part in such a manner as toinvolve two similar amines, i. e., the aldehyde may react with twomolecules of the hydroxylated amine; it may react with one mole of thehydroxylated amine and one mole of the non-hydroxylated amine; or it mayunite with two moles of the nonhydroxylated amine. In such event as lastmentioned, the resultant compound is without value, unless a hydroxyaldehyde, such as aldol, has been employed. In such event, an attempt toesterify with a detergent-monocarboxy acid results in the formation ofan entirely different type of material, i. e., an acid radical beingintroduced into the aldehyde radical or residue as differentiated fromthe amine radical residue; and in fact, one must esterify with ahydroxylated fatty acid or its equivalent, that is, ricinoleic acid, ifone intends to obtain a product which is subsequently susceptible toesterification with phthalic anhydride or the like, which is not ob-,-jectionable, and is, in fact, of value for the various purposes hereinenumerated, but is not contemplated within the hereto attached claims.For practical purposes, then, it is most expedient to manufacture orproduce a methylene di amine from a single kind of secondary amine; andin such event, obviously it must be a hydroxylated amine, such asdiethanolamine. In subsequent examples, diethanolamine is employed asthe secondary amine for reaction with the aldehyde; but in view of whathas been said previously, various other secondary amines or mixturesthereof might be employed.

Attention is again directed to the fact that wherever a hydroxyl radicalexists, and provided it is not necessary for subsequent reaction, thensuch hydroxyl radical could be reacted with an acid, such as aceticacid, butyric acid, heptoic acid, etc.; and this statement applies tothe hydroxyl radical of an alcohol aldehyde, such as aldol. Furthermore,an alkylol radical might be so combined as has been previously pointedout, or the alcohol radical or its equivalent might be combined with amonohydric alcohol. In essence, such combination simply results in thehydrocarbon chain interrupted at least once by an oxygen atom, asdifferentiated from an uninterrupted hydrocarbon chain. In the heretoappended claims reference to an alkyl alkylol or similar radical isintended specifically to include such examples where there isinterruption of the chain or ring by an oxygen atom. All hydroxylradicals present may be acylated except one, and if at least one of theacylating acids is a hydroxy acid, such as ricinoleic acid, then in thatevent, all hydroxyl radicals may be acylated.

The composition of matter herein contemplated is obtained, as has beenpreviously pointed out, by reaction between amines of the kinddescribed, and polybasic acids or their obvious equivalent, such as theanhydrides or acyl chlorides or the like; and included among the variouspolybasic acids which may be used are: phthalic, succinic, malic,fumaric, citric, maleic, adipic, tartaric, gluteric, diphenic,naphthalic, oxalic, chlorphthalic, nitrophthalic, etc., some of whichhave three carboxyl radicals.

Having obtained the hydroxylated tertiary acylated methylene diamine ofthe kind previously described in an anhydrous state, reaction with thepolybasic carboxy acid takes place rapidly and is nothing more than anesterification reaction comparable in nature to reactions betweenphthalic anhydride and glycerol, or ethylene glycol, diethylene glycol,diglycerol, diethanolamine,

triethanolamine, or the like, all of which are well known. Theconditions of reaction are substantially the same as employed in thetypes of reaction just enumerated.

Our preferred reagent is obtained in the following manner:

We react a readily available aldehyde, such as acetaldehyde orheptaldehyde, in the molecular proportions of one mole of aldehyde withtwo moles of diethanolamine. Such reaction is conducted in the mannerpreviously noted; and after completion of reaction, any water stillpresent which has not been removed previously in the course of reactionis removed by distillation, preferably under vacuum.

Such hydroxylated diamine is then treated in the proportion of threemoles of diamine to two moles of castor oil, which consists essentiallyof triricinolein. Any suitable quantity of material may be employed, forinstance, 500 lbs. of the selected anhydrous diamine and the appropriateamount of castor oil. The two products are mixed together and heated ata reasonable temperature above the boiling point of water and below thepoint of decomposition, for instance, at some temperature between135-175 C. for a suitable period of time, i, e., l to 5 hours. Theproduct so obtained is the acylated diamine mixed with some freeglycerol and certain other accompanying cogeneric products.

Our preference is to conduct the esterification reaction in the sameapparatus as employed for the alcoholysis reaction just referred to. Inother words, having prepared the acylated diamine, we add a suitablequantity of phthalic anhydride.

Generally speaking, our preference is to employ an equal weight, orpreferably an excess, such as 50% more phthalic anhydride by weight,than the equivalent quantity of diethanolamine employed in preparing thediamine. Naturally,'the amount of phthalic anhydride is dependent, inpart, on whether or not a hydroxylated fatty acid, such as ricinoleic,was used for acylation. The esterification reaction is conducted in theconventional manner until all free phthalic anhydride has disappeared.The product so obtained is suitable for use as a demulsifier for oilfield emulsions.

The tertiary methylene diamine of the kind described may be considered,for the sake of simplicity, as being in the class of an alcohol, i. e.,a monohydric or polyhydric alcohol. If an alcohol is indicated by theformula Y(OH)1., where 71 indicates the number one or more, and if apolybasic acid be indicated by the formula X(COOH) 11,, where nindicates the number 2 or more, then the reactions between a monohydricalcohol and a polybasic acid will result in a compound which may beindicated by the following formula: YX(COOH)n, where 11. indicates thenumber one or more, and which is, in reality, a contraction of a moreelaborate structural formula, in which X and Y are joined by a carboxylradical or residue. Assuming, however, as would be true in the majorityof cases, that the alcohol actually would be a polyhydric alcohol, thenexamination reveals that the formula might result in a combination, inwhich there were neither residual carboxyl radicals, nor residualhydroxyl radicals, or might result in compounds in which there wereresidual hydroxyl radicals and no residual carboxyl radicals, orcompounds where there might be residual carboxyl radicals and noresidual hydroxyl radicals;

or there might be both. This is indicated by the following:

in which q indicates a small whole number (one in the case of a monomerand probably not over 20 and usually less than and m and n indicate thenumber one or more, and m and 71." indicate a small or moderately-sizedwhole number, such as 0, 1 or more, but in any event, probably a numbernot in excess of 40; for instance, as would be indicated by a moleculewhich involved 10 to 15, or perhaps 20 moles of methylene diaminederived from aldol and diglycerylamine. Naturally, each residualhydroxyl could be combined with phthalic anhydride, so as to give atleast one free carboxyl; or if combined with a tribasic acid, such ascitric acid, the number of free carboxyls, might approach severalhundred; for instance, 400 or 500 at least. Actually, the preferabletype of reagent would be more apt to contain less than 20, and in fact,less than 10 free hydroxyl radicals. It is not necessary to remark thatresidual carboxyl radicals can be permitted to remain as such, or can beneutralized in any suitable manner, such as conversion into salts,esters, amides, amino esters, or any other suitable form. Usually, suchconversion into salt form would be by means of sodium hydroxide,potassium hydroxide, calcium hydroxide, magnesium hydroxide, ammoniumhydroxide, amylamine, butanolamine, ethanolamine, diethanolamine,triethanolamine, cyclohexanolamine, benzylamine, aniline, toluidine,etc. Conversion into the ester would be by means of a monohydricalcohol, such as methyl alcohol, ethyl alcohol, propyl alcohol, butylalcohol, hexyl alcohol, octyl alcohol, decyl alcohol, ethylene glycol,diethylene glycol, glycerol, diglycerol, triethylene glycol, or thelike, or one might employ a hydroxylated fatty acid, such as ricinoleicacid, or its ester, such as ethyl ricinoleate or triricinolein as analcohol, 1. e., in such a manner that reaction would involve the alcoholhydroxyl radical. Naturally, if desired, the polybasic acid, such ascitric or phthalic anhydride, may be reacted with a selected body, so asto form a fractional ester, and such fractional ester may be employed,instead of the acid, followed by subsequent esterification. Thus, onemay employ triricinolein monophthalate, or the di-phthalate, ricinoleicacid monophthalate, ethyl hydroxystearate monophthalate, di-stearinmonophthalate, di-naphthenin monophthalate, di-abietin monophthalate,etc.

If a tricarboxy acid, such as citric acid, is employed, then at leasttheoretically, three moles of the tertiary methylene diamine might reactwith one mole of citric acid. Similarly, as has already been pointedout, at least seventeen moles of a polybasic acid might be combined witha highly hydroxylated methylene amine. For practical purposes, however,we have found that the most desirable products are obtained bycombinations, in which the ratio of the alcoholic diamine to thepolybasic acid is within the ratio of three to one and one to five, andin which the molecular weight of the resultant product does not exceed10,000, and is usually less than 5,000, or perhaps less than 3,000. Thisis particularly true if the resultant product is soluble to a fairlydefinite extent, for instance, at least 5% in some solvent, such aswater, alcohol, benzene, dichlorethyl ether, acetone, cresylic acid, orthe like. This is simply another way of stating that it is preferablethat the product be of the sub-resinous type, which is commonly referredto as an A resin or a B resin, as distinguished from a C resin, which isa highly infusible, insoluble resin (see Ellis, Chemistry of SyntheticResins (1935), pages 862, et seq.).

In recapitulating what has been said previously, the sub-resinous,semi-resinous, or resinous product herein contemplated may be indicatedby the following formula:

in which the characters have their previous significance, and yrepresents a small whole number not greater than 3, and 3: represents asmall whole number not greater than Z represents a hydrogen ionequivalent, such as a metallic atom, organic radical, etc.

A One must not lose sight of the fact that the product hereincontemplated is a basic amine. This means, of course, that the productcan combine with acids to form salts; for instance, it may combine withacetic acid, hydrochloric acid, oxalic acid, phthalic acid, butyricacid, naphtheni-c acid, etc. To state the matter another Way, the hereincontemplated amine, if desired, may be dissolved in a dilute acid, suchas 5% of acetic acid, 5% sulfuric acid, 5% nitric acid, or the like. Theamine may be used as such, or as an aqueous solution-which in essence,represents the corresponding diammonium base. In other words, allreferences herein to the final product, and particularly in the appendedclaims, contemplate not only the amine itself, but the correspondingsalts or double salts, the corresponding base or double base, thecorresponding salt base mixture, or similar variations, which may beindicated from this viewpoint solely by the following monomeric typeformulas:

gmzl g :112]? 510512;][5 new]: momz 5 2 imomz 5 2:

All that has been said previously can be recast in a single formula, inview of the following consideration: The aldehyde employed may beindicated by the following formula:

in which T represents a hydrogen atom or ZT. In the last mentionedsituation, T represents a divalent hydrocarbon radical, and Z representsa hydrogen atom, a hydroxyl radical, an R.COO radical, i. e., anoxy-acyl radical derived from a detergent-forming monocarboxy acid, anOH.RCOO radical, i. e., a special type of detergent-forming monocarboxyacid, to wit, a hydroxylated one, such as ricinoleic acid,hydroxynaphthenic acid, hydroxy abietic acid, or the like; or it mayrepresent RCOO,' an oXy-acyl radical derived from a monobasic carbo-xyacid having 7 carbon atoms or less, such as heptoic acid, acetic acid,etc. Such aldehyde combines with two moles of an acylated amine, or withtwo moles of an amine, which may be subsequently acylated with adetergent-forming acid to give an intermediate amine, which may beindicated by the following formula:

in which all the characters have their previous significance, B being adivalent hydrocarbon radical, which may be interrupted at least once byan oxygen atom, m representing the number 1 or 2, m representing thenumber 1, 2 or 3, and B' representing a monovalent hydrocarbon radical,which may be interrupted at least once by oxygen. A, A, A" and Arepresent the numbers 0, 1, 2 3 or l, with the proviso that A+A'+A"+A"shall equal 4; and there must be present at least one alcoholic hydroxylradical.

For the sake of simplicity, it is pointed out once more that ZTcollectively may represent a hydrogen atom, instead of a methyl radical,for instance, and that it is contemplated that in the hereto attachedclaims formaldehyde, having only the hydrogen atom attached to thecarbon atom,

shall be considered as the obvious functional" equivalent ofacetaldehyde, etc. It has been previously pointed out that an effort torecognize this minor differentiation in the structural formula producesa further step or complication in nomenclature.

The final composition of matter herein contemplated may be characterizedfor the sake of simplicity in the following manner,.and it is to benoted that certain subletters are hereafter changed for purposes ofsimplification:

in which all of the characters have their previous significance, to wit,B being a divalent hydrocarbon radical, which may be interrupted atleast once by an oxygen atom, and may have a hydroxyl radical as anintegral part thereof, m"

type:

representing the number 1 or 2, m representing the number 1, 2 or 3, andB' representing a monovalent hydrocarbon radical, which may beinterrupted at least once by oxygen; A, A, A"

and A' represent the numbers 0, 1, 2, 3 or 4,

with the proviso that A+A+A"+A"' shall equal 4; and there must bepresent at least one alcoholic hydroxyl radical as a part of thediamine; ZT collectively may represent a hydrogen atom, instead of amethyl radical, for example; and X is a residue or radical derived froma polybasic carboxy acid.

When aldehydes and secondary amines react, in addition to the tertiarymethylene diamine, 155 there may be formed minor by-products, such aspolymeric forms and the like. Similarly, it is possible that otherby-products or cogeneric compounds are formed in the subsequentreactions previously described. As far as demulsification of crude oilsor similar purposes are concerned, it is quite probable that thepresence of such cogeneric materials is not objectionable, but may bedesirable. Therefore, in order to define completelythe metes and boundsof the present invention, it is deemed advisable to characterize thefinal product not only by means of the formula above described, but alsoin terms of the steps of manufacture. It is obvious that certainalternate forms of the steps of manufacture may be employed, but theywould be the obvious equivalents of the steps indicated. For instance,the polybasic carboxy acid, such as phthalic acid, might be combinedwith ricinoleic acid, and such material employed for acylation of thetertiary methylene diamine. However, such obvious variation is theequivalent of the steps or procedure herein indicated. One might acylatea secondary alkylol amine, such as diethanolamine, and employ suchcompound for reaction with the selected aldehyde.

It is believed that the principal product of reaction previouslydescribed is obtained through the formation of an intermediate commonlyreferred to as a pseudo-basic carbinal. See J ou nal of the ChemicalSociety, volume 119, 1921, page 1470, and also volume 123, 1923, page532. The formation of the intermediate may be indicated thus:

where DH is a molecule having a labile hydrogen atom. Such products arepseudo-carbinols, and in the event that D is connected to the carbonatom by means of a nitrogen atom, for instance, where D was derived fromdiethanolamine, then the previous formula becomes:

and compounds which carry the linkage NtoH l are commonly referred to aspseudo-basic carv binols.

One recognized property of the pseudo-basic carbinols is the avidity ofthe hydroxyl radical for a labile hydrogen atom. Thus, the aboveintermediate would immediately react with a second molecule ofdiethanolamine to form the diamine previously described. This is'indicated in the following manner: f

Such being the probable course of reaction, it is obvious thatconsiderable insight is disclosed as to the nature of the accompanyingcogeneric materials which are present in the mixture. In other words,one would expect tofind material in which the hydrogen atom was removedfrom other sources, as, for instance, a hydrogen of the hydroxyl of anethanol radical, etc.

In our divisional application Serial No. 300,8 l2 filed Oct. 23, 1939,We have described a novel process for resolving or breaking petroleumemulsions of the water-in-oil type. Said process involves subjecting theemulsion to the action of a demulsifier consisting of the abovedescribed new material or composition of matter. Said mate rial is usedeither alone, or in admixture with another, or with other conventionaldemulsifying agents; and its method of use is the same as that generallyemployed in resolving or breaking petroleum emulsions of thewater-in-oil type with a chemical demulsifier. Briefly stated, theconventional method of using a chemical demulsifier to break a petroleumemulsion consists in introducing the demulsifier into the well in whichthe emulsion is produced; introducing the demulsifier into a conduitthrough which the emulsion is flowing; or introducing the demulsifierinto a tank in which the emulsion is stored. After treatment theemulsion is allowed to stand in a quiescent state, usually in a settlingtank, and usually at a temperature varying from atmospheric temperatureto about 200 F., so as to permit the water or brine to separate from theoil, it being preferable to keep the temperature low enough to preventthe volatilization of valuable constituents of the oil. The amount ofdemulsifier that may be required to break the emulsion may vary from 1part of demulsifier to 500 parts of emulsion, up to 1 part ofdemulsifier to 20,000 or even 30,000. parts of emulsion.

We desire to point out that the superiority of the reagent ordemulsifying agent herein described is based upon its ability to treatcertain emulsions more advantageously and at a somewhat lower cost thanis possible with other available demulsifiers, or conventional mixturesthereof. Itis believed said demulsifying agent or treating agent willfind comparatively limited application, so far as the majority of oilfield emulsions are concerned; but we have found that such ademulsifying agent has commercial value, as it will economically breakor resolve oil field emulsions in a number of cases which cannot betreated as easily or at so low a cost with the demulsifying agentsheretofore available.

Having thus described our invention, what we claim as new and desire tosecure by Letters Patent is:

1. An esterification reaction product of: (A)- carbon atoms and not morethan 32 carbon atoms.

2. An esterification reaction product of: (A)

a polybasic carboxy acid; and (B) a hydroxylated diamine derived byreaction between: first, a

secondary'amine free from aryl radicals; and

second, an aldehyde, followed by subsequently subjecting said aminealdehyde reaction product to an acylation reaction involving an acidcompound derived from a detergent-forming acid having not lessthan 8carbon atoms and not more than 32 carbon atoms.

3. A method of making a new composition of matter, characterized byreacting under conditions such as to cause esterification: (A) apolybasic carboxy acid; and (B) a hydroxylated diamine derived byreaction between: first, a secondary amine; and second, an aldehyde, andsaid amine aldehyde reaction product being subsequently subjected to anacylation reaction involving an acid compound derived from adetergent-forming acid having not less than 8 carbon atoms and not morethan 32 carbon atoms.

4. A method of making a new composition of matter, characterized byreacting under conditions such as to cause: (A) a polybasic carboxyacid; and (B) a hydroxylated diamine derived 1 prising an esterificationreaction product of the formula type:

- (coon)...

( )1|( y z')q in which X is a radical derived from a polybasic carboxyacid and 1 represents a small whole number not greater than 3, and :0represents a I small Whole number not greater than 5, and n,

m, and m indicate small whole numbers such as 0-, 1, or more, but in anyevent a number not in excess of 40; q indicates a small whole number notover 20; Z is a hydrogen ion equivalent; Y is a radical derived from ahydroxylated acylated tertiary methylene diamine obtained by reactionbetween: first, a secondary amine; and

second, an aldehyde, followed by subsequentlyv subjecting said aminealdehyde reaction product to an acylated reaction involving an acidcompound derived from a detergent-forming acid having not less than 8carbon atoms and not more than 32 carbon atoms.

6. A sub-resinous composition of matter, comprising an esterificationreaction product of the formula type:

in which X is a radical derived from a polybasic carboxy acid and 1represents a small whole number not greater than 3, and :c' represents asmall whole number not greater than 5, and n, m, and m indicate smallwhole numbers such as 0, 1, or more, but in any event a number not inexcess of 40; q indicates a small whole number not over 20; Z is ahydrogen ion equivalent; Y is a radical derived from a hydroxylatedacylated tertiary methylene diamine obtained by (0H)n( ')q 0002).. inwhich X is a radical derived from a polybasic carboxy acid and 1represents a small whole number not greater than 3, and m represents asmall whole number not greater than 5, and n,

. m, and m indicate small whole numbers such atoms.

8. A sub-resinous composition of matter, comprising an esterificationreaction product of the formula type:

inwhich X is a radical derived from a polybasic carboxy acid and :11represents a small whole number not greater than 3, and ar represents asmallwholenumber not greater than 5, and n,

m, and m indicate small whole numbers such as 7 0, 1, or more, but inany event a number not in excess of 40; q indicates a small whole numbernot over 20; Z is a hydrogen ion equivalent; Y is a radical derived fromhydroxylated acylated tertiary methylene diamine obtained by reactionbetween: first, diethanolamine and second, an aldehyde, followed bysubsequently subjecting said amine reaction product to an acylationreaction involving an acid compound derived from a detergent-formingacid having not less than 8 carbon atoms and not more than 32 carbonatoms.

9. A sub-resinous composition of matter, comprising an esterificationreaction product of the formula type:

in which X is a radical derived from a polybasic carboxy acid and 11'represents a small whole number not greater than 3, and :11 represents asmall whole number not greater than 5, and n, m, and m indicate smallwhole numbers such as 0, 1, or more, but in any event a number not inexcess'of 40; q indicates a small whole number not over 20; Z is ahydrogen ion equivalent; Y is a radical derived from hydroxylatedacylated tertiary methylene diamine obtained by reaction between: first,diethanolamine; second, an aldehyde, followed by subsequentlysubjecting'said amine reaction product to an acylation reactioninvolving an acid compound derived from a fatty acid.

10. A sub-resinous composition of matter, comprising an esterifiedreaction product of the formula type:

in which X is a radical derived from a polybasic carboxy acid and yrepresents a small whole 25 involving an acid compound derived from anunsaturated fatty acid.

11. A sub-resinous composition of matter, comprising an esterific-ationreaction product f 30' the formula type:

( y z)q 35 in which X is a radical derived from a polybasic carboxylicacid and 1 represents a small whole number not greater than 3, and 0:represents a small whole number not greater than 5, and n, m, and mindicate small whole numbers such as 40 0, 1, or more, but in any eventa number not in excess .of 40; q indicates a small whole number not over20; Z is a hydrogen ion equivalent; Y is a radical derived fromhydroxylated acylated tertiary methylene diamine obtained by reaction 45between: first, diethanolamine; second, an aldehyde, followed bysubsequently subjecting said amine reaction product to an acylationreaction involving an acid compound derived from a hydroxylatedunsaturated fatty acid.

12. A sub-resinous composition of matter, comprising an esterificationreaction product of the formula type:

in which X is a radical derived from a polybasic carboxylic acid and 1,!represents a small whole number not greater than 3, and x represents asmall whole number not greater than 5, and n, m, and m indicate smallwhole numbers such as 0, 1, or more, but in any event a number not inexcess of 40; q indicates a small whole number not over 20; Z is ahydrogen ion equivalent; Y is a radical derived from hydroxylatedacylated tertiary methylene diamine obtained by reaction between: first,diethanolamine; second, an aldehyde, free from an alkyl radicalcontaining more than 2 carbon atoms.

13. A sub-resinous composition of matter,

in which X is a radical derived from a polybasic carboxylic acid and yrepresents a small whole number not greater than 3, and :11 represents asmall whole number not greater than 5, and n, m, and m indicate smallwhole numbers such as 0, 1, or more, but in any event a number not inexcess of 40; q indicates a small whole number not over 20; Z is ahydrogen ion equivalent; Y is a radical diamine obtained by reactionbetween: first, diethanolamine; second, acetaldehyde, followed bysubsequently subjecting said amine aldehyde reaction product toacylation reaction involving ricinoleic acid.

MELVIN DE GROOTE. BERNHARD KEISER. ARTHUR F. WIRTEL.

